CN102614894B - Supported catalyst used for synthesis of diisopropylamine from isopropylamine and preparation method as well as application of supported catalyst - Google Patents

Supported catalyst used for synthesis of diisopropylamine from isopropylamine and preparation method as well as application of supported catalyst Download PDF

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CN102614894B
CN102614894B CN2012100545324A CN201210054532A CN102614894B CN 102614894 B CN102614894 B CN 102614894B CN 2012100545324 A CN2012100545324 A CN 2012100545324A CN 201210054532 A CN201210054532 A CN 201210054532A CN 102614894 B CN102614894 B CN 102614894B
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supported catalyst
platinum
nickel
copper
catalyst
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冯烈
陈云斌
钱晔
黄佳民
钱超
陈新志
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ZHEJIANG JIANYE CHEMICAL CO Ltd
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ZHEJIANG JIANYE CHEMICAL CO Ltd
Zhejiang University ZJU
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Abstract

本发明公开了一种用于异丙胺合成二异丙胺的负载型催化剂，以焙烧后γ-氧化铝为载体，在载体上负载活性组分，得负载型催化剂；活性组分由镍、铜和铂组成；镍、铜、铂和焙烧后γ-Al2O3的重量之和称为总重，镍占总重的15～25％，铜占总重的5～12％，铂占总重的0.5～1％。本发明还同时提供了上述负载型催化剂的制备方法。本发明还同时提供了上述负载型催化剂的用途：用于将异丙胺合成二异丙胺。在异丙胺歧化反应合成二异丙胺的过程中使用本发明的负载型催化剂，具有环境友好、毒性低、与其他工艺相比成本大大降低、适用于工业化生产等特点。

The invention discloses a supported catalyst for synthesizing diisopropylamine from isopropylamine, which uses calcined gamma-alumina as a carrier, and loads an active component on the carrier to obtain a supported catalyst; the active component consists of nickel, copper and Composition of platinum; the sum of the weight of nickel, copper, platinum and γ- Al2O3 after roasting is called the total weight, nickel accounts for 15-25% of the total weight, copper accounts for 5-12% of the total weight, and platinum accounts for the total weight 0.5-1% of the total. The present invention also provides a preparation method for the above-mentioned supported catalyst. The present invention also simultaneously provides the use of the above-mentioned supported catalyst: for synthesizing diisopropylamine from isopropylamine. Using the supported catalyst of the present invention in the process of synthesizing diisopropylamine through the disproportionation reaction of isopropylamine has the characteristics of environmental friendliness, low toxicity, greatly reduced cost compared with other techniques, and suitability for industrialized production.

Description

The loaded catalyst and method for making and the purposes that are used for the synthetic diisopropylamine of isopropylamine
Technical field
The present invention relates to loaded catalyst of the synthetic diisopropylamine of a kind of isopropylamine disproportionated reaction and its production and use.
Background technology
Diisopropylamine (Diisopropylamine), its molecular formula are C 6H 15N, its structural formula is as follows:
Figure BDA0000140450380000011
Diisopropylamine is a kind of important fine chemistry intermediate, be mainly used in synthetic pesticide, herbicide etc., secondly for the synthesis of medical diisopropyl amine dichloro acetate, diisopropylamine ascorbate, practolol and propantheline, in addition, also for the synthesis of dyestuff, thiofide, surfactant etc.
The report that synthesizes the catalyst of diisopropylamine about isopropylamine by disproportionated reaction in document mainly contains two kinds, is respectively K/H β zeolite-A l 2O 3Catalyst and ZrO 2/ H β zeolite-A l 2O 3Catalyst.Specific as follows:
1), patent CN1148341C has reported with K/H β zeolite-A l 2O 3For the synthetic diisopropylamine of catalyst isopropylamine, H β zeolite 50～95wt% wherein, potassium is 0.2～4.0wt%, surplus is γ-Al 2O 3Catalyst breakage is become 8～20 orders, get in a certain amount of stainless steel reactor of packing into, react for upper feeding, reactant flows out from reactor bottom, 200～300 ℃ of reaction temperatures, reaction pressure normal pressure～0.8MPa, air speed 0.2～1.5h -1Obtain finally the conversion ratio 10～25% of isopropylamine, diisopropylamine selectively all more than 99%,, although this catalyst is selective good, make the conversion ratio of isopropylamine very low because catalytic activity is not high.
2), patent CN1127373C has reported with ZrO 2/ H β zeolite-A l 2O 3For catalyst, H β zeolite 20～90wt% wherein, zirconia is 2.0～15.0wt%, surplus is γ-Al 2O 3200～300 ℃ of reaction temperatures, pressure are normal pressure～0.8MPa, air speed 0.2～1.0h -1This reaction isopropylamine conversion ratio with K/H β zeolite-A l 2O 3For the situation of catalyst similar, neither be very high, selectively will be slightly lower than K/H β zeolite-A l 2O 3Catalyst.In addition, use zr element in this catalyst, expensive more a lot of than copper nickel element commonly used on general industry, so this catalyst is difficult for heavy industrialization.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of activity is high, cost is low, selective high loaded catalyst that is used for the synthetic diisopropylamine of isopropylamine and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of loaded catalyst for the synthetic diisopropylamine of isopropylamine, take gama-alumina after roasting as carrier, load active component on carrier, obtain loaded catalyst; Active component is comprised of nickel, copper and platinum; γ-Al after nickel, copper, platinum and roasting 2O 3The weight sum be called gross weight, described nickel accounts for 15～25% of gross weight, copper accounts for 5～12% of gross weight, platinum accounts for 0.5～1% of gross weight.
After above-mentioned roasting, gama-alumina can be taked the following methods preparation: with gama-alumina (γ-Al 2O 3) prior to 400～500 ℃ of roasting 1.5～2.5h, then in 550～600 ℃ of roasting 4.5～5.5h; γ-Al after roasting 2O 3After testing: after this roasting, the specific area of gama-alumina is about 190～200m 2/ g, aperture is 15.0～15.8nm.Gama-alumina (γ-Al 2O 3) be common commercially available prod, its particle diameter is 2～3mm.The remarks explanation: after roasting, the particle diameter of gama-alumina is equal to the particle diameter of gama-alumina (before being roasting) substantially.
The present invention also provides the preparation method of above-mentioned loaded catalyst for the synthetic diisopropylamine of isopropylamine simultaneously, comprises the following steps:
1), biscuit firing:
With gama-alumina (γ-Al 2O 3) prior to 400～500 ℃ of roasting 1.5～2.5h, then in 550～600 ℃ of roasting 4.5～5.5h; γ-Al after roasting 2O 3
2), with step 1) γ-Al after the roasting of gained 2O 3With water retting at least 36 hours, then measure the volume that water reduces, thereby γ-Al after roasting 2O 3Pore volume density (that is, pore volume);
3), first dipping:
Nickel salt, mantoquita and platinum salt are dissolved in water (for example being distilled water), obtain mixed solution; With step 1) γ-Al after the roasting of gained 2O 3Impregnated in mixed solution γ-Al after roasting 2O 3Pore volume be 1/2～1.1/2 (the best is 1/2) of mixed liquor volume, dip time equals step 2) dip time; γ-Al after platinum in nickel in nickel salt, the copper in mantoquita, platinum salt and roasting 2O 3The weight sum be called gross weight, the nickel in nickel salt accounts for 15～25% of gross weight, the copper in mantoquita accounts for 5～12% of gross weight, the platinum in platinum salt accounts for 0.5～1% of gross weight;
After dipping finishes, filter, obtain filtrate and solid, solid is catalyst;
4), after baking:
With step 3) catalyst of gained is in 40～60 ℃ of dryings 1.5～2.5 hours (being preferably 50 ℃ of dryings 2 hours), then in 260～300 ℃ of roastings 5～7 hours (being preferably 280 ℃ of roastings 6 hours), more naturally is cooled to room temperature;
5), double-steeping:
With step 4) catalyst of gained puts into step 3) the filtrate dipping of gained is until filtrate is all absorbed (approximately 20～28h);
6), step 5) catalyst of gained is in 75～95 ℃ of dryings 1.5～2.5 hours (being preferably 85 ℃ of dryings 2 hours), then in 430～470 ℃ of roastings 5～7 hours, more naturally is cooled to room temperature; Must be used for the loaded catalyst by the synthetic diisopropylamine of isopropylamine.
Further improvement as the preparation method of the loaded catalyst for the synthetic diisopropylamine of isopropylamine of the present invention: nickel salt is nickel nitrate, and mantoquita is copper nitrate, and platinum salt is platinum nitrate.
The present invention also provides the method for utilizing the synthetic diisopropylamine of above-mentioned loaded catalyst simultaneously, carries out successively following steps:
1), loaded catalyst is activated, must activate back loading type catalyst; Activation back loading type catalyst is placed in fixed bed reactors;
2), will be placed in head tank as the isopropylamine of material liquid, utilize at the uniform velocity sample introduction of sampling pump, the material liquid vaporization is rear by containing the fixed bed reactors of activation back loading type catalyst, face hydrogen amine disproportionated reaction with the activation back loading type catalyst in fixed bed reactors, the volume space velocity of material liquid is 0.1～0.25h -1, it is 0.7～1.1Mpa that the adjusting hydrogen pressure makes the pressure of fixed bed reactors, the fixed bed reaction actuator temperature is 200～240 ℃;
3), collect step 2) product of gained carries out atmospheric distillation, obtains diisopropylamine (collecting the cut of 84 ℃～86 ℃).
Improvement as the method for synthetic diisopropylamine of the present invention: loaded catalyst is activated and comprises the following steps step 1):
1), loaded catalyst is carried out primary activation, duration of ventilation, ventilation flow rate and heating-up temperature in different soak time sections during primary activation are as shown in table 1 below:
Table 1
Figure BDA0000140450380000031
2), the loaded catalyst after primary activation is being activated under the hydrogen effect again between 100～250 ℃, until evaporated condensation water produces; Must activate back loading type catalyst.
In the method for synthetic diisopropylamine of the present invention:
Figure BDA0000140450380000032
The remarks explanation: above-mentioned catalyst refers to loaded catalyst, and the stereomutation amount of loaded catalyst before and after activation almost do not have, and this very little variable can be ignored.
Be used for the synthetic diisopropylamine of isopropylamine disproportionated reaction after loaded catalyst activation of the present invention.During the synthetic diisopropylamine of isopropylamine disproportionated reaction, reaction is carried out under hydro condition, and reaction temperature is 200～240 ℃, reaction pressure 0.7～1.1MPa, and the volume space velocity of reactant (isopropylamine) is 0.1～0.25h -1Volume space velocity=isopropylamine volume flow (m 3/ h)/catalyst volume (m 3).That is the copper on the catalyst that, uses in reaction, nickel, platinum have been simple substance.
In the present invention, loaded catalyst prepares gained (being that catalyzed dose of metal salt solution absorbs fully) by equi-volume impregnating, its process comprises the roasting of carrier, with aquametry pore volume density, the metal salt solution of preparation two volumes, 2 dippings of carrier and slaine, dry, roasting process.
Use loaded catalyst of the present invention in the process of the synthetic diisopropylamine of isopropylamine disproportionated reaction, have the following advantages:
(1), avoided the generation of water from source, thereby the appearance of having avoided a series of azeotropic relevant with water to form has alleviated the burden of separating greatly.
(2), this catalyst activity high, selectively good, cost is low.
(3), the preparation method of loaded catalyst of the present invention has the characteristics such as raw material sources are extensive, simple to operate; Use loaded catalyst of the present invention in the process of the synthetic diisopropylamine of isopropylamine disproportionated reaction, have environmental friendliness, toxicity low, compare cost with other techniques and greatly reduce, be applicable to the characteristics such as suitability for industrialized production.
Description of drawings
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the schematic diagram of the present invention for the synthesis of the device of diisopropylamine.
The specific embodiment
The preparation method of embodiment 1, a kind of loaded catalyst for the synthetic diisopropylamine of isopropylamine, carry out following steps successively:
1), biscuit firing:
With commercially available γ-Al 2O 3(particle diameter is 2～3mm) to put into Muffle furnace at 400～500 ℃ of roasting 2h, then in 550～600 ℃ of roasting 5h; γ-Al after roasting 2O 3
After testing: γ-Al after roasting 2O 3Specific area be 190～200m 2/ g, aperture is 15.0～15.8nm, particle diameter remains unchanged substantially.
2), with step 1) γ-Al after the roasting of gained 2O 3With water retting 36 hours, then measure the volume that water reduces, the volume that water reduces is γ-Al after roasting 2O 3Pore volume; γ-Al after roasting 2O 3Pore volume density (being pore volume) be 0.9ml/g.
3), first dipping:
66.8g six water nickel nitrates, 27.8g nitrate trihydrate copper and 0.9g platinum nitrate are dissolved in distilled water, then water (for example for distilled water) is settled to 104.4mL, obtains mixed solution; With step 1) γ-Al after the roasting of gained 2O 358g impregnated in mixed solution and (that is, to make γ-Al after roasting 2O 3Pore volume be mixed liquor volume 1/2); Dip time is 36 hours;
After dipping finishes, filter, obtain filtrate and solid, solid is catalyst;
4), after baking:
With step 3) catalyst of gained is in 50 ℃ of dryings 2 hours, then in Muffle furnace in 280 ℃ of roastings 6 hours, more naturally be cooled to room temperature;
5), double-steeping:
With step 4) catalyst of gained puts into step 3) filtrate of gained floods 24h, this moment step 3) catalyzed dose of the filtrate of gained all absorbs.
6), step 5) catalyst of gained is in 85 ℃ of dryings 2 hours, then in Muffle furnace in 450 ℃ of roastings 6 hours, more naturally be cooled to room temperature; The loaded catalyst that must be used for the synthetic diisopropylamine of isopropylamine.
In this loaded catalyst, contained Ni, Cu and Pt are about respectively 17%, 9%, 0.6% (W/W) (with simple substance form, calculating).
Remarks explanation: γ-Al after roasting 2O 3Weight, the weight of nickel element in six water nickel nitrates, in nitrate trihydrate copper in the weight of copper and platinum nitrate the weight sum of platinum element be gross weight, copper, nickel, the weight of platinum element, respectively divided by gross weight, namely obtains above-mentioned three % by weight.
The production method of experiment 1, a kind of diisopropylamine, use device as shown in Figure 1, carries out successively following steps:
1), loaded catalyst is activated, comprise following 2 steps:
1., first carry out primary activation, during primary activation shown in duration of ventilation, ventilation flow rate and the heating-up temperature table 1 as mentioned in the above of different soak time sections; This step can be carried out outside fixed bed reactors, also can utilize fixed bed reactors (but need to add N 2Connecting pipe).
2., the loaded catalyst after primary activation is loaded in fixed bed reactors and again activates in 100～250 ℃ (being for example 150～200 ℃) under the hydrogen effect, until evaporated condensation water produces; Must activate back loading type catalyst.
At this moment, the cupric oxide in loaded catalyst, nickel oxide and platinum oxide all change into copper, nickel, platinum accordingly.
Certainly, above-mentioned activation processing also can be carried out elsewhere, then will activate rear catalyst and be packed in fixed bed reactors.
2), 355g (6mol) isopropylamine is placed in head tank as material liquid, utilize at the uniform velocity sample introduction of sampling pump, isopropylamine by the vaporizer that is arranged in the fixed bed reactors top after (effect of vaporizer be make isopropylamine gasification) face hydrogen amine disproportionated reaction (H with the activation back loading type catalyst (also can be described as beds) of fixed bed reactors 2By entering in fixed bed reactors after vaporizer), the volume space velocity of material liquid (isopropylamine) is 0.15h -1It is 0.9Mpa that the adjusting hydrogen pressure makes the pressure in fixed bed reactors, and beds (that is, in fixed bed reactors) temperature is controlled to be 220 ℃, reacted product is collected with liquid form after the condensation of condenser, reaction is analyzed and carry out step 3 after finishing) atmospheric distillation.
3), the product that will collect carries out atmospheric distillation, the cut of collecting 33 ℃ is unreacted isopropylamine, can again recycle.The cut of collecting 84 ℃～86 ℃ is diisopropylamine, obtains product diisopropylamine 185.1g, and the conversion ratio of isopropylamine is 61.1%, and diisopropylamine is selectively 99.6%.
Products therefrom is correct through characterizing structure.
Change the volume space velocity of load capacity, reaction temperature, reaction pressure and the material liquid of copper nickel platinum on catalyst in experiment 1; All the other steps, with experiment 1, obtain respectively testing 2～experiment 21.The conversion ratio of the isopropylamine of gained and diisopropylamine selectively as shown in table 2.
Table 2
Figure BDA0000140450380000061
Figure BDA0000140450380000071
Annotate: the preparation method of the loaded catalyst of experiment 2～experiment 21, step 3 except embodiment 1) consumption of six water nickel nitrates, nitrate trihydrate copper and the platinum nitrate of first dipping carries out the correspondence change according to the copper content in table 2, nickel content, platinum content respectively, and all the other are all with embodiment 1.
Contrast test, the load capacity (as shown in table 3) of copper nickel platinum on catalyst in experiment 1 that change, all the other are with testing 1; Must contrast 1～contrast 5; Acquired results is as shown in table 3.
Table 3
Figure BDA0000140450380000072
Annotate: the preparation method of the loaded catalyst of contrast 1～contrast 5, step 3 except embodiment 1) consumption of six water nickel nitrates, nitrate trihydrate copper and the platinum nitrate of first dipping carries out the correspondence change according to the copper content in table 3, nickel content, platinum content respectively, and all the other are all with embodiment 1.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.

Claims (5)

1.用于异丙胺合成二异丙胺的负载型催化剂，其特征是：以焙烧后γ-氧化铝为载体，在所述载体上负载活性组分，得负载型催化剂；所述活性组分由镍、铜和铂组成；所述镍、铜、铂和焙烧后γ-Al2O3的重量之和称为总重，所述镍占总重的15～25%，铜占总重的5～12%，铂占总重的0.5～1%。1. the supported catalyst that is used for synthesizing diisopropylamine from isopropylamine is characterized in that: take gamma-alumina after roasting as carrier, load active component on described carrier, obtain supported catalyst; Described active component is made of Composition of nickel, copper and platinum; the sum of the weight of the nickel, copper, platinum and γ-Al 2 O 3 after firing is called the total weight, the nickel accounts for 15% to 25% of the total weight, and the copper accounts for 5% of the total weight. ~12%, platinum accounts for 0.5~1% of the total weight. 2.如权利要求1所述的用于异丙胺合成二异丙胺的负载型催化剂的制备方法，其特征是包括以下步骤：2. the preparation method of the supported catalyst that is used for synthesizing diisopropylamine from isopropylamine as claimed in claim 1 is characterized in that comprising the following steps: 1）、初次焙烧：1), initial roasting: 将γ-氧化铝先于400~500℃焙烧1.5~2.5h，然后于550~600℃焙烧4.5~5.5h；得焙烧后γ-Al2O3；Roast γ-alumina at 400~500°C for 1.5~2.5h, then at 550~600°C for 4.5~5.5h; get γ-Al 2 O 3 after roasting; 2）、将步骤1）所得的焙烧后γ-Al2O3用水浸渍至少36小时，然后测定水减少的体积，从而得焙烧后γ-Al2O3的孔体积密度；2) Immerse the calcined γ-Al 2 O 3 obtained in step 1) with water for at least 36 hours, and then measure the volume of water reduction, so as to obtain the pore volume density of the calcined γ-Al 2 O 3 ; 3）、初次浸渍：3), initial impregnation: 将镍盐、铜盐和铂盐溶解于水中，得混合溶液；将步骤1）所得的焙烧后γ-Al2O3浸渍于混合溶液中，所述焙烧后γ-Al2O3的孔体积为混合溶液体积的1/2~1.1/2，浸渍时间等于步骤2）的浸渍时间；所述镍盐中的镍、铜盐中的铜、铂盐中的铂和焙烧后γ-Al2O3的重量之和称为总重，所述镍盐中的镍占总重的15～25%，铜盐中的铜占总重的5～12%，铂盐中的铂占总重的0.5～1%；Dissolving nickel salt, copper salt and platinum salt in water to obtain a mixed solution; immersing the roasted γ-Al 2 O 3 obtained in step 1) in the mixed solution, the pore volume of the roasted γ-Al 2 O 3 1/2~1.1/2 of the volume of the mixed solution, and the immersion time is equal to the immersion time of step 2); the nickel in the nickel salt, the copper in the copper salt, the platinum in the platinum salt and the γ-Al 2 O after roasting The sum of the weights of 3 is called the total weight, the nickel in the nickel salt accounts for 15-25% of the total weight, the copper in the copper salt accounts for 5-12% of the total weight, and the platinum in the platinum salt accounts for 0.5% of the total weight. ~1%; 浸渍结束后，过滤，得滤液和固体，所述固体为催化剂；After the impregnation is finished, filter to obtain a filtrate and a solid, and the solid is a catalyst; 4）、二次焙烧：4), secondary roasting: 将步骤3）所得的催化剂于40~60℃干燥1.5~2.5小时，然后于260~300℃焙烧5~7小时，再自然降温至室温；Dry the catalyst obtained in step 3) at 40-60°C for 1.5-2.5 hours, then roast at 260-300°C for 5-7 hours, and then cool down to room temperature naturally; 5）、二次浸渍：5), the second impregnation: 将步骤4）所得的催化剂放入步骤3）所得的滤液中浸渍直至滤液被全部吸收；Put the catalyst obtained in step 4) into the filtrate obtained in step 3) and soak until the filtrate is completely absorbed; 6）、步骤5）所得的催化剂于75~95℃干燥1.5~2.5小时，然后于430~470℃焙烧5~7小时，再自然降温至室温；得用于由异丙胺合成二异丙胺的负载型催化剂。6) The catalyst obtained in step 5) was dried at 75~95°C for 1.5~2.5 hours, then calcined at 430~470°C for 5~7 hours, and then naturally cooled to room temperature; it was used as a support for the synthesis of diisopropylamine from isopropylamine type catalyst. 3.根据权利要求2所述的用于异丙胺合成二异丙胺的负载型催化剂的制备方法，其特征是：所述镍盐为硝酸镍，铜盐为硝酸铜，铂盐为硝酸铂。3. the preparation method of the supported catalyst that is used to synthesize diisopropylamine from isopropylamine according to claim 2 is characterized in that: the nickel salt is nickel nitrate, the copper salt is copper nitrate, and the platinum salt is platinum nitrate. 4.利用如权利要求1所述的负载型催化剂合成二异丙胺的方法，其特征是：依次进行以下步骤：4. utilize the method for the synthetic diisopropylamine of supported catalyst as claimed in claim 1, it is characterized in that: carry out following steps successively: 1）、将负载型催化剂进行活化，得活化后负载型催化剂；活化后负载型催化剂被置于固定床反应器中；1) Activate the supported catalyst to obtain an activated supported catalyst; the activated supported catalyst is placed in a fixed-bed reactor; 2）、将作为原料液的异丙胺置于原料罐中，利用进样泵匀速进样，原料液汽化后通过含有活化后负载型催化剂的固定床反应器，与固定床反应器中的活化后负载型催化剂进行临氢胺歧化反应，原料液的体积空速为0.1~0.25h-1，调节氢压使固定床反应器的压力为0.7~1.1Mpa，固定床反应器温度为200~240℃；2) Put the isopropylamine as the raw material liquid in the raw material tank, and use the sampling pump to inject the sample at a constant speed. After the raw material liquid is vaporized, it passes through the fixed-bed reactor containing the activated supported catalyst, and the activated The supported catalyst carries out the disproportionation reaction of hydrogenated amine, the volume space velocity of the raw material liquid is 0.1~0.25h -1 , the hydrogen pressure is adjusted so that the pressure of the fixed bed reactor is 0.7~1.1Mpa, and the temperature of the fixed bed reactor is 200~240℃ ; 3）、收集步骤2）所得的产物进行常压精馏，得二异丙胺。3) Collect the product obtained in step 2) and perform atmospheric distillation to obtain diisopropylamine. 5.根据权利要求4所述的合成二异丙胺的方法，其特征是：步骤1）的将负载型催化剂进行活化包括以下步骤：5. The method for synthesizing diisopropylamine according to claim 4, characterized in that: step 1) activating the supported catalyst comprises the following steps: 1）、将负载型催化剂进行初步活化，初步活化的时间总计为24h，依次进行下表所述的时间段；所述初步活化时在不同活化时间段的通气时间、通气流量和加热温度如下表所示：1) Preliminary activation of the supported catalyst, the initial activation time is 24 hours in total, and the time periods described in the table below are carried out in sequence; the ventilation time, ventilation flow rate and heating temperature in different activation time periods during the preliminary activation are shown in the table below Shown:
Figure FDA0000336722041
Figure FDA0000336722041
 2）、将初步活化后的负载型催化剂在氢气作用下于100～250℃进行再次活化，直至无冷凝水产生；得活化后负载型催化剂。2) The pre-activated supported catalyst is reactivated under the action of hydrogen at 100-250°C until no condensed water is produced; the activated supported catalyst is obtained.
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